JPS6227556B2 - - Google Patents
Info
- Publication number
- JPS6227556B2 JPS6227556B2 JP57224011A JP22401182A JPS6227556B2 JP S6227556 B2 JPS6227556 B2 JP S6227556B2 JP 57224011 A JP57224011 A JP 57224011A JP 22401182 A JP22401182 A JP 22401182A JP S6227556 B2 JPS6227556 B2 JP S6227556B2
- Authority
- JP
- Japan
- Prior art keywords
- furnace
- cds
- cdte
- flux
- firing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000010304 firing Methods 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 16
- 229910004613 CdTe Inorganic materials 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 10
- 230000004907 flux Effects 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 6
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- 238000010030 laminating Methods 0.000 claims 1
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 12
- 238000000034 method Methods 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 239000000758 substrate Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000002411 adverse Effects 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1828—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/543—Solar cells from Group II-VI materials
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Photovoltaic Devices (AREA)
Description
【発明の詳細な説明】
産業上の利用分野
本発明は太陽電池などに使用可能なCdS／
CdTe構造の光起電力素子の製造方法に関するも
のである。[Detailed Description of the Invention] Industrial Application Field The present invention provides CdS/
The present invention relates to a method for manufacturing a photovoltaic device having a CdTe structure.
従来例の構成とその問題点
すでに知られているように、CdS／CdTe構造
の光起電力素子の製造方法として、ガラス基板上
にｎ形CdS焼結膜を形成し、その上に（Cd＋
Te）粉と、融剤として作用する塩化カドミウム
と粘結剤を加えて混合し、泥状にしたものをスク
リーン印刷し、これを有孔蓋付きアルミナボート
に入れベルトコンベア式連続焼成炉で温度600℃
近傍の不活性ガスを含む雰囲気中で焼成すること
によつてCdTe焼結膜を形成するものがある。Structure of the conventional example and its problems As is already known, as a method for manufacturing a photovoltaic element with a CdS/CdTe structure, an n-type CdS sintered film is formed on a glass substrate, and (Cd+
Te) powder, cadmium chloride that acts as a flux, and a binder are mixed, the slurry is screen printed, and this is placed in an alumina boat with a perforated lid and heated in a belt conveyor type continuous firing furnace. 600℃
There is a method in which a CdTe sintered film is formed by firing in an atmosphere containing nearby inert gas.
上記方法において、融剤として添加した塩化カ
ドミウムは、焼成中温度上昇と共に融解し、徐々
に蒸発しながらCdTeの結晶成長作用を行い、焼
成が終了した時点ではほとんど塩化カドミウムは
存在しなくなることが望ましい。 In the above method, it is desirable that the cadmium chloride added as a flux melts as the temperature rises during firing and gradually evaporates to grow CdTe crystals, so that by the time firing is complete, almost no cadmium chloride exists. .
従来の自然排気での焼成方法では、塩化カドミ
ウムが蒸発して炉内で滞留し、連続焼成の場合、
後続の素子は炉内に滞留している塩化カドミウム
等の影響を受け、焼成の順序によつては特性の悪
い結晶膜が出来る欠点がある。またこれ以外にも
ガラス基板が黒くなつたり、あるいは炉内の雰囲
気が変化して焼成不充分の形となつてCdTe粉が
はがれたりして特性に悪影響を及ぼし、再現性及
び量産焼成が出来ない欠点がある。 In the conventional firing method using natural exhaust, cadmium chloride evaporates and remains in the furnace, and in the case of continuous firing,
Subsequent elements are affected by cadmium chloride, etc. remaining in the furnace, and depending on the firing order, a crystal film with poor characteristics may be produced. In addition to this, the glass substrate may turn black, or the atmosphere inside the furnace may change, resulting in insufficient firing and the CdTe powder may peel off, which adversely affects the properties, making reproducibility and mass production firing impossible. There are drawbacks.
発明の目的
本発明の目的は、前述の欠点を除去して連続焼
成の場合にも後続する素子に悪影響を与えず、特
性値が均一で再現性のよい素子が得られる光起電
力素子の製造方法を提供することにある。Purpose of the Invention The purpose of the present invention is to manufacture a photovoltaic device that eliminates the above-mentioned drawbacks, does not adversely affect subsequent devices even in the case of continuous firing, and provides devices with uniform characteristic values and good reproducibility. The purpose is to provide a method.
発明の構成
本発明の製造方法は、CdS焼結膜上にCdとTe
の粉末および融剤を含むペーストを塗布した後、
これを半気密性ボートに入れ、ベルトコンベア式
連続焼成炉を用い、不活性ガス雰囲気中におい
て、炉内に発生する融剤ガスを前記不活性ガスの
流量に対して20〜40％の排気量で強制排気しなが
ら焼結するものである。Structure of the Invention The manufacturing method of the present invention provides Cd and Te on a CdS sintered film.
After applying a paste containing powder and flux of
This is placed in a semi-airtight boat, and in an inert gas atmosphere using a belt conveyor type continuous firing furnace, the flux gas generated in the furnace is pumped out at a rate of 20 to 40% of the flow rate of the inert gas. Sintering is performed under forced exhaust air.
以下本発明の製造方法について図面を参照しな
がら具体的に説明する。 The manufacturing method of the present invention will be specifically explained below with reference to the drawings.
第１図は本発明に用いるベルトコンベア式連続
焼成炉の全体構成を示す断面図である。同図にお
いて、焼成炉はヒータ１１によつて中央部が約
620℃となるように設定炉入口カーテン外側１、
炉入口カーテン内側２、炉内中央３、炉出口カー
テン内側４、炉出口カーテン外側５にそれぞれ同
流量が流されている。この炉内へガラス基板上に
CdSをスクリーン印刷して焼結し、更にこの上
に、Cd粉、Te粉、塩化カドミウムおよび粘結剤
からなる混合物をスクリーン印刷または塗布し、
100℃にて乾燥後有孔蓋付きアルミナボート６に
入れ、連続的にベルト７に乗せ、ベルトスピード
２〜４cm／minの速さで炉内に送り込む。炉内に
送り込まれた有孔蓋付きアルミナボート６内で
は、温度上昇とともに塩化カドミウムが溶解を始
め、さらに蒸発して蒸気となる。これによつて
CdTeの結晶成長が進行して焼結膜が出来る。塩
化カドミウム蒸気は、アルミナボートの蓋の孔を
通り、炉内に滞留してN2ガス中に混入する。連
続焼結をするにつれて炉内の塩化カドミウムの蒸
気の濃度は高くなり、CdTe焼結膜に悪影響を与
えて、従来例で述べたような欠点が生じる。 FIG. 1 is a sectional view showing the overall configuration of a belt conveyor type continuous firing furnace used in the present invention. In the same figure, the central part of the firing furnace is heated by the heater 11.
Furnace entrance curtain outside 1, set to 620℃
The same flow rate is applied to the inside of the furnace inlet curtain 2, the center of the furnace 3, the inside of the furnace exit curtain 4, and the outside of the furnace exit curtain 5, respectively. into this furnace onto the glass substrate
CdS is screen printed and sintered, and then a mixture of Cd powder, Te powder, cadmium chloride and a binder is screen printed or applied on top of this,
After drying at 100°C, it is placed in an alumina boat 6 with a perforated lid, placed continuously on a belt 7, and fed into a furnace at a belt speed of 2 to 4 cm/min. In the alumina boat 6 with a perforated lid sent into the furnace, cadmium chloride begins to melt as the temperature rises and further evaporates to become steam. Due to this
CdTe crystal growth progresses and a sintered film is formed. Cadmium chloride vapor passes through a hole in the lid of the alumina boat, stays in the furnace, and mixes with the N2 gas. As the sintering continues, the concentration of cadmium chloride vapor in the furnace increases, which adversely affects the CdTe sintered film, resulting in the drawbacks described in the conventional example.
このため本発明では、炉内に滞留する塩化カド
ミウムその他の蒸気を炉外に強制排気する方法を
採つている。すなわち、第１図に示す炉内の上部
に、数箇所に吸い込み孔のある排気用ガス管８を
取り付け、その排気用ガス管８を流量計９につな
ぎ、さらにこれをアスピレータ、真空ポンプ等
（図示せず）に連結している。この装置によつて
炉内のガスを強制排気させ、炉内を一定にクリー
ニングが出来ると共に、排気量を制御することが
出来る。 For this reason, the present invention employs a method of forcibly exhausting cadmium chloride and other vapors remaining in the furnace to the outside of the furnace. That is, an exhaust gas pipe 8 with suction holes at several locations is attached to the upper part of the furnace shown in FIG. (not shown). With this device, the gas inside the furnace can be forcibly exhausted, the inside of the furnace can be constantly cleaned, and the amount of exhaust gas can be controlled.
実施例の説明
次に本発明の実施例を比較例と対比しながら説
明をする。Description of Examples Next, examples of the present invention will be described while comparing them with comparative examples.
比較例 １
ガラス基板上に、スクリーン印刷法でCdS粉末
に塩化カドミウムを添加したCdSペーストを塗布
してCdS層を形成し、これを約690℃で焼成して
CdS焼結膜を作成した。次にその上にCdTe粉100
ｇに対して融剤として塩化カドミウムを0.5ｇを
加え、さらに粘結剤を加えてCdTeペーストを作
成し、これをCdS焼結膜上にスクリーン印刷し
た。印刷後乾燥機を用い、100℃の温度で30分
間、不要の有機溶媒を蒸発させて除去した。Comparative Example 1 A CdS paste made by adding cadmium chloride to CdS powder was applied on a glass substrate using a screen printing method to form a CdS layer, and this was baked at approximately 690°C.
A CdS sintered film was created. Then add 100% CdTe powder on top of that.
0.5 g of cadmium chloride as a flux was added to 1.5 g of cadmium chloride as a flux, and a binder was further added to prepare a CdTe paste, which was screen printed on the CdS sintered film. After printing, unnecessary organic solvent was removed by evaporation using a dryer at a temperature of 100° C. for 30 minutes.
次に、第１図のベルトコンベア式連続焼成炉に
より焼結を行つた。焼結条件は、炉内中央部温度
を620℃とし、炉入口カーテン外側１、炉入口カ
ーテン内側２、炉内中央３、炉出口カーテン内側
４、炉出口カーテン外側５に設けられた各ガス管
孔よりN2ガスを毎分定量に流し、排気ガス管８
より、真空ポンプで炉内中央部のガスを排気し
た。排気径路途中で流量計９と排気量調節コツク
を設け、排気量は、N2ガス100／minに対して
12／minの流量にした。そして印刷乾燥させた
基板を有孔蓋付きアルミナボート６中に入れ、ベ
ルト７上にアルミナボート６を３列に並べ、ベル
トスピードを毎分３cmとして焼結を行なつた。 Next, sintering was performed using a belt conveyor type continuous sintering furnace shown in FIG. The sintering conditions were as follows: the temperature at the center of the furnace was 620°C, and each gas pipe was installed at the outside of the furnace entrance curtain 1, inside the furnace entrance curtain 2, inside the furnace center 3, inside the furnace exit curtain 4, and outside the furnace exit curtain 5. Flow N2 gas through the hole at a fixed rate every minute, and exhaust gas pipe 8
Then, the gas in the center of the furnace was evacuated using a vacuum pump. A flow meter 9 and an exhaust volume adjustment knob are installed in the middle of the exhaust route, and the exhaust volume is set to 100/min for N2 gas.
The flow rate was set to 12/min. Then, the printed and dried substrate was placed in an alumina boat 6 with a perforated lid, the alumina boats 6 were arranged in three rows on a belt 7, and sintering was performed at a belt speed of 3 cm/min.
このようにして得られた素子は、次にCdTe上
にカーボン電極、さらにその上にAgペーストを
スクリーン印刷した。またCdS膜上には（Ag＋
In）ペーストを印刷し、これらを種々の条件で熱
処理した。 The device thus obtained was then screen-printed with carbon electrodes on CdTe, and then with Ag paste on top of the carbon electrodes. Moreover, on the CdS film (Ag+
In) Pastes were printed and these were heat treated under various conditions.
このような方法で得られた素子は、焼結順によ
る特性値のばらつきがあり、強制排気の効果はな
かつた。 Elements obtained by such a method had variations in characteristic values depending on the order of sintering, and forced evacuation had no effect.
実施例 １
大要は上記比較例１と変りがないが、異なる点
は、強制排気量を多くした点である。比較例１で
は、強制排気量はN2ガス100／minに対して12
／minとしたが、本実施例では、これをさらに
多くして強制排気量を20／minとした。強制排
気量を多くすることにより、比較例１より排気効
果が出て、焼結順序による素子特性値のばらつき
が小さくなつた。同時に基板の変色もなくなつ
た。Example 1 The outline is the same as Comparative Example 1, but the difference is that the forced exhaust amount was increased. In Comparative Example 1, the forced exhaust amount was 12 for N2 gas 100/min.
/min, but in this example, this was further increased to make the forced displacement amount 20/min. By increasing the forced evacuation amount, the evacuation effect was more effective than in Comparative Example 1, and the variation in element characteristic values due to the sintering order was reduced. At the same time, the discoloration of the board disappeared.
実施例 ２
比較例１および実施例１と異なる点は、強制排
気量をさらに多くした点である。本実施例では、
強制排気量をN2ガス100／minに対して32／
minとしたが、さらには排気効果が出て、焼成順
序による素子特性のばらつきが著しく改善され、
基板の変化もなくなり、外観もよくなつた。Example 2 The difference from Comparative Example 1 and Example 1 is that the forced exhaust amount was further increased. In this example,
Forced exhaust volume is 32/min for N2 gas 100/min.
In addition, an exhaust effect was obtained, and the variation in device characteristics due to the firing order was significantly improved.
There are no changes to the board, and the appearance has improved.
比較例 ２
比較例１および実施例１、２と異なる点は強制
排気量をさらに多くした点である。本比較例では
N2ガス流量100／minに対して強制排気量を50
／minとした。この場合には、強制排気量が多
いために炉内の不活性雰囲気濃度が不足しCdTe
焼結膜が酸化した。Comparative Example 2 The difference from Comparative Example 1 and Examples 1 and 2 is that the forced exhaust amount was further increased. In this comparative example
Forced exhaust amount is 50 for N2 gas flow rate 100/min.
/min. In this case, the inert atmosphere concentration in the furnace is insufficient due to the large amount of forced evacuation, and the CdTe
The sintered film was oxidized.
第２図および第３図に上記各実施例および比較
例で得られた素子の実用変換効率ηPをCdTe膜
の焼結順に示した。第２図中Ａは従来の方法、Ｂ
は比較例１、第３図中Ｃは実施例１、Ｄは実施例
２、Ｅは比較例２のそれぞれの測定値である。 FIGS. 2 and 3 show the practical conversion efficiency η P of the devices obtained in each of the above examples and comparative examples in the order of sintering of the CdTe film. In Figure 2, A is the conventional method, B
In FIG. 3, C is the measured value of Example 1, D is Example 2, and E is the measured value of Comparative Example 2.
第２図および第３図から明らかなように、本実
施例で得られた素子の実用変換効率ηPは焼成の
順序に関係なく均一で再現性のよい素子が実現で
きた。 As is clear from FIGS. 2 and 3, the practical conversion efficiency η P of the device obtained in this example was uniform and had good reproducibility regardless of the firing order.
発明の効果
以上の説明から明らかなように、本発明の製造
法は炉内に発生する融剤ガス等を不活性ガスの流
量に対応した所定の流量で強制排気するものであ
り、ベルトコンベア炉による焼成順の特性ばらつ
きがなくなるために量産が可能になり、更には焼
成膜の色が一定となるために素子の外観が良好と
なる。Effects of the Invention As is clear from the above explanation, the manufacturing method of the present invention is for forcibly exhausting the flux gas etc. generated in the furnace at a predetermined flow rate corresponding to the flow rate of the inert gas. Since variations in characteristics due to the firing order are eliminated, mass production becomes possible, and furthermore, the color of the fired film becomes constant, resulting in a good appearance of the device.
第１図は本発明に用いるベルトコンベア式連続
焼成炉の全体構成を示す断面図、第２図および第
３図は本発明の実施例および比較例で得られた素
子の実用変換効率を示す特性図である。
６……有孔蓋付きアルミナボート、７……ベル
ト、８，１２……ガス管、９……流量計、１０…
…カーテン、１１……ヒータ。
Figure 1 is a sectional view showing the overall configuration of a belt conveyor type continuous firing furnace used in the present invention, and Figures 2 and 3 are characteristics showing practical conversion efficiency of elements obtained in Examples and Comparative Examples of the present invention. It is a diagram. 6... Alumina boat with perforated lid, 7... Belt, 8, 12... Gas pipe, 9... Flow meter, 10...
...Curtain, 11...Heater.
Claims (1)
CdTe焼結膜を積層して光起電力素子を製造する
に際し、前記CdS焼結膜上とCdとTeの粉末およ
び融剤を含むペーストを塗布した後、これを半気
密性ボートに入れ、ベルトコンベア式連続焼成炉
を用い、不活性ガス雰囲気中において、炉内に発
生する融剤ガスを前記不活性ガスの流量に対して
20〜40％の排気量で強制排気しながら焼結するこ
とを特徴とする光起電力素子の製造方法。1 CdS sintered film and
When manufacturing a photovoltaic device by laminating CdTe sintered films, a paste containing Cd and Te powders and a flux is applied to the CdS sintered film, and then placed in a semi-airtight boat, which is then conveyed using a belt conveyor. Using a continuous firing furnace, in an inert gas atmosphere, the flux gas generated in the furnace is adjusted to the flow rate of the inert gas.
A method for producing a photovoltaic element, characterized by sintering while forcedly evacuation at a volume of 20 to 40%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57224011A JPS59115569A (en) | 1982-12-22 | 1982-12-22 | Manufacture of photovoltaic element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57224011A JPS59115569A (en) | 1982-12-22 | 1982-12-22 | Manufacture of photovoltaic element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59115569A JPS59115569A (en) | 1984-07-04 |
| JPS6227556B2 true JPS6227556B2 (en) | 1987-06-15 |
Family
ID=16807184
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57224011A Granted JPS59115569A (en) | 1982-12-22 | 1982-12-22 | Manufacture of photovoltaic element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59115569A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61187281A (en) * | 1985-02-14 | 1986-08-20 | Matsushita Electric Ind Co Ltd | Manufacture of solar cell |
| EP0853345B1 (en) * | 1996-05-28 | 2004-02-18 | Matsushita Battery Industrial Co Ltd | METHOD FOR FORMING CdTe FILM |
| ITUD20050196A1 (en) * | 2005-11-17 | 2007-05-18 | Gisulfo Baccini | EQUIPMENT FOR THE PRODUCTION OF THIN PHOTOVOLTAIC CELLS IN SILICON AND OF ELECTRONIC CIRCUITS IN RIGID AND FLEXIBLE MATERIAL |
| CN102261838A (en) * | 2011-05-31 | 2011-11-30 | 江苏顺风光电科技有限公司 | Caterpillar band for sintering furnace of solar cells |
-
1982
- 1982-12-22 JP JP57224011A patent/JPS59115569A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59115569A (en) | 1984-07-04 |
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